DE19859720A1 - Agent for dyeing keratin fibers - Google Patents

Abstract

The invention relates to an agent for dying keratin fibers, especially human hair. The inventive agent contains a naphthyl-azo compound with formula (I), in which R<1> represents hydrogen, halogen, hydroxy, nitro, a C1-C4-alkyl group, a C1-C4-alkoxy group, sulfo group or carboxy group; R<2> represents a 1- or 2-naphthyl group which comprises at least one hydroxy group and, as additional substituents, can comprise hydroxy groups, sulfo groups, carboxy groups, nitro groups or halogen atoms, or represents a 1-aryl-5-hydroxy-4-pyrazolyl radical which can be substituted in position 3 by a C1-C4-group; M represents hydrogen, an alkali metal or 1/2 alkaline earth metal, 1/3 Al(III), 1/2 Zn(II), 1/4 Ti(IV), 1/4 Zr(IV), 1/3 Cr(III), 1/2 Co(II), 1/2 Fe(II), 1/3 Mo(III) or 1/6 Mo(VI), 1/3 W(III) or 1/6 W(VI) or ammonium.

Description

The invention relates in particular to an agent for dyeing fibers containing keratin whose human hair contains certain naphthyl azo compounds, the use of these compounds as a coloring component in hair dyeing as well as a method for dyeing keratin fibers, in particular human hair.

For dyeing keratin fibers, e.g. B. hair, wool or furs, generally come either direct dyes or oxidation dyes substances by oxidative coupling of one or more developer components with each other or with one or more coupler components Application. Coupler and developer components are also called oxidation called dye precursors.

Primary aromatic amines are usually used as developer components another free or substituted one in the para or ortho position Hydroxy or amino group, diaminopyridine derivatives, heterocyclic hydrazones, 4-aminopyrazolone derivatives and 2,4,5,6-tetraaminopyrimidine and its deri vate used.

Specific representatives are, for example, p-phenylenediamine, p-toluenediamine, 2,4,5,6-tetraaminopyrimidine, p-aminophenol, N, N-bis (2-hydroxyethyl) -p-pheny lendiamine, 2- (2,5-diaminophenyl) ethanol, 2- (2,5-diaminophenoxy) ethanol, 1- Phenyl-3-carboxyamido-4-amino-pyrazolon-5, 4-amino-3-methylphenol, 2-amino methyl-4-aminophenol, 2-hydroxymethyl-4-aminophenol, 2-hydroxy-4,5,6-tria  minopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine and 2,5,6-triamino-4-hydroxy pyrimidine.

As coupler components, m-phenylenediamine derivatives, naph tholes, resorcinol and resorcinol derivatives, pyrazolones, m-aminophenols and substi tuiert pyridine derivatives used. Particularly suitable as coupler substances other α-naphthol, 1,5-, 2,7- and 1,7-dihydroxynaphthalene, 5-amino-2-methylphe nol, m-aminophenol, resorcinol, resorcinol monomethyl ether, m-phenylenediamine, 2,4-diaminophenoxyethanol, 2-amino-4- (2-hydroxyethylamino) anisole (Lehmanns Blue), 1-phenyl-3-methyl-pyrazolon-5, 2,4-dichloro-3-aminophenol, 1,3-bis- (2,4- diaminophenoxy) propane, 2-chlororesorcinol, 4-chlororesorcinol, 2-chloro-6-methyl-3- aminophenol, 2-methylresorcinol, 5-methylresorcinol, 3-amino-6-methoxy-2-methyl aminopyridine and 3,5-diamino-2,6-dimethoxypyridine.

With regard to other common dye components, it is expressly stated "Dermatology", edited by Ch. Culnan, H. Maibach, publisher Marcel Dekker Inc., New York, Basel, 1986, vol. 7, Ch. Zviak, The Science of Hair Care, chap. 7, Pages 248-250 (direct dyes), and chap. 8, pages 264-267 (Oxi dation dyes), as well as the "European inventory of cosmetic raw materials", 1996, published by the European Commission, available in disk form by the Federal Association of German Industry and Commerce for Arz neimittel, health products and personal care e. V., Mannheim, reference genom men.

With oxidation dyes intensive dyeings can be achieved with good fastness properties, but the development of the color is usually done under the influence of oxidizing agents such. B. H ₂ O ₂ , which in some cases can lead to damage to the fiber. Furthermore, some oxidation dye precursors or certain mixtures of oxidation dye precursors can sometimes have a sensitizing effect on people with sensitive skin. Di rectifying dyes are applied under gentler conditions, but their disadvantage is that the dyeings often have inadequate fastness properties.

The use of the combination of 2-hydroxy-4- described in more detail below sulfo-1-naphthyl-azo compounds with special metal salts of the 2nd or 3rd Main group of the periodic table and / or salts of the transition metals to Dyeing fibers containing keratin is not yet known.

The object of the present invention is to provide dyes for keratin fibers, in particular for human hair, which are qualitatively at least equivalent to the usual oxidation hair dyes in terms of color depth, gray coverage and fastness properties, but without necessarily relying on oxidizing agents such as e.g. B. H ₂ O _{2 to be} instructed. In addition, the colorants may have no or only a very low sensitization potential.

Surprisingly, it has now been found that those shown in formula I. 2-hydroxy-4-sulfo-1-naphthyl-azo compounds alone as well as in combination with certain MetaN salts are found even in the absence of oxidizing agents excellent for dyeing keratin fibers. They result from colorations with excellent brilliance and depth of color and lead to diverse Shades of color. However, the use of oxidizing agents is not intended be partially excluded.

The invention relates to an agent for dyeing keratin fibers, especially human hair containing naphthyl azo compounds Formula I,  

in which R ^{1 represents} hydrogen, halogen, hydroxy, nitro, a C ₁ -C ₄ alkyl group, a C ₁ -C ₄ alkoxy group, sulfo group or carboxy group, R ^{2 represents} a 1- or 2-naphthyl group which has at least one hydroxyl group carries and as further substituents may have hydroxyl, sulfo, carboxy, nitro groups or halogen atoms, or for a 1-aryl-5-hydroxy-4-py razolylrest, which is in the 3-position by a C ₁ -C ₄ group M is hydrogen, an alkali or 1/2 alkaline earth metal, 1/3 AI (111), 1/2 Zn (II), 1/4 Ti (IV), 1/4 Zr (IV) , 1/3 Cr (111), 1/2 Co (II), 1/2 Fe (II), 1/3 Mo (III) or 1/6 Mo (Vl), 1/3 W (III) resp 1/6 W (VI) or ammonium.

Among keratin fibers are wool, furs, feathers and in particular understand human hair. The colorants according to the invention can in principle, but also for dyeing other natural fibers, such as. B. cotton, jute, Sisal, linen or silk, modified natural fibers, such as. B. regenerated cellulose, Nitro, alkyl or hydroxyalkyl or acetyl cellulose and synthetic fibers, such as B. polyamide, polyacrylonitrile, polyurethane and polyester fibers used become.

The compounds of the formula I are preferably selected from the group following azo compounds: eriochrome black A, eriochrome black T, hydroxy naphthol blue, acid blue 158, eriochrome red B, eriochrome red R and acid red 186.

These substances are known from the literature or are commercially available.  

The above-mentioned azo compounds with the formula I are in the inventions Agents according to the invention usually in an amount of 0.03 to 65 mmol, esp special from 1 to 40 mmol, based on 100 g of the total colorant, ent hold.

They can be used as direct dyes or in the presence of other com components are used.

Colorants containing the azo compound with the formula I alone, be preferred for coloring in the range of red, red-violet, blue-violet and red-brown set.

An expansion of the color nuances and improvement of the intensity can be achieved if the azo compounds with the formula I in combination with Metalsal zen of the 2nd and 3rd main group of the periodic table and / or salts of the Über gear metals are used. The compounds of formula I and the Me tall salts are preferably in a molar ratio in this embodiment from 0.5: 1 to 2: 1.

The metal salts which are preferably used are preferably selected from the chlorides, sulfates, acetates, lactates and nitrates of Ca, Mg, Al (III), Zn (II), Ti (IV), Zr (IV), Cr (III), Co (II), Fe (II), Mo (III, VI), W (III, VI).

On the presence of oxidizing agents, e.g. B. H ₂ O ₂ , who can do without. However, it can It may be desirable to add hydrogen peroxide or other oxidizing agents to the agents according to the invention to achieve the shades which are lighter than the keratin-containing fiber to be colored. Oxidizing agents are usually used in an amount of 0.01 to 6 wt .-%, based on the application solution. A preferred oxidizing agent for human hair is H ₂ O ₂ .

In a preferred embodiment, the dyes according to the invention contain means for further modification of the color shades in addition to the invention contained compounds in addition usual oxidation dye precursors, ins special selected from the above compounds, and / or directly drawing dyes, e.g. B. from the group of nitrophenylenediamines, nitroamino phenols, anthraquinones or indophenols, such as. B. the international one Designations or trade names HC Yellow 2, HC Yellow 4, HC Yellow 6, Basic Yellow 57, Disperse Orange 3, HC Red 3, HC Red BN, Basic Red 76, HC Blue 2, Disperse Blue 3, Basic Blue 99, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Disperse Black 9, Basic Brown 16 and Basic Brown 17 known ver bonds and picramic acid 2-amino-6-chloro-4-nitrophenol, 4-amino-2-nitro diphenylamine-2'-carboxylic acid, 6-nitro-1,2,3,4-tetrahydroquinoxaline, 4-N-ethyl-1,4- bis (2'-hydroxyethylamino) -2-nitrobenzene hydrochloride and 1-methyl-3-nitro-4- (2'- hydroxyethyl) aminobenzene. The agents according to this embodiment form, the substantive dyes preferably contain in an amount of 0.01 to 20 wt .-%, based on the total colorant.

Furthermore, the preparations according to the invention can also be used in nature upcoming dyes such as henna red, henna neutral, henna black, chamomile flower, sandalwood, black tea, sapwood, sage, Contains blue wood, madder root, catechu, sedre and alkanna root.

It is not necessary for the components used to be uniform Represent connections. Rather, in the dye according to the invention due to the manufacturing process for the individual dyes, in un minor quantities may also contain further components, insofar as these do not adversely affect the coloring result or for other reasons, e.g. B. toxicological, must be excluded.

The colorants according to the invention already result in physiologically tolerable Chen temperatures of below 45 ° C intense colorings. They are therefore suitable especially for coloring human hair. For use on the  Human hair can usually be dyed in a water-based cosmetic carriers are incorporated. Suitable water-based cosmetic Carriers are e.g. B. creams, emulsions, gels or surfactant-containing foaming Solutions such as B. shampoos or other preparations suitable for use on the keratin fibers are suitable. If necessary, it is also possible Lich to incorporate the colorants in anhydrous carriers.

Furthermore, the colorants according to the invention can all be prepared in such a way contain known active ingredients, additives and auxiliaries. In many cases included the colorants at least one surfactant, in principle both anionic and also zwitterionic, ampholytic, nonionic and cationic surfactants are suitable. In many cases, however, the surfactants have proven to be advantageous select from anionic, zwitterionic or nonionic surfactants.

Suitable anionic surfactants in preparations according to the invention are all anionic surface-active substances suitable for use on the human body. These are characterized by a water-solubilizing, anionic group such as. B. a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group with about 10 to 22 carbon atoms. In addition, the molecule can contain glycol or polyglycol ether groups, ester, ether and amide groups and hydroxyl groups. Examples of suitable anionic surfactants are, in each case in the form of the sodium, potassium and ammonium and the mono-, di- and trialkanolammonium salts with 2 or 3 carbon atoms in the alkanol group

• - linear fatty acids with 10 to 22 carbon atoms (soaps),
• Ether carboxylic acids of the formula RO- (CH ₂ -CH ₂ O) x -CH ₂ COOH, in which R is a linear alkyl group with 10 to 22 C atoms and x = 0 or 1 to 16,
• Acyl sarcosides with 10 to 18 carbon atoms in the acyl group,
• Acyl taurides with 10 to 18 carbon atoms in the acyl group,
• Acyl isethionates with 10 to 18 carbon atoms in the acyl group,  
• - Sulfosuccinic acid and dialkyl esters with 8 to 18 carbon atoms in the Al alkyl group and sulfosuccinic acid mono-alkyl polyoxyethyl ester with 8 to 18 Carbon atoms in the alkyl group and 1 to 6 oxyethyl groups,
• Linear alkanesulfonates with 12 to 18 carbon atoms,
• Linear alpha-olefin sulfonates with 12 to 18 carbon atoms,
• - Alpha-sulfofatty acid methyl esters of fatty acids with 12 to 18 carbon atoms,
• Alkyl sulfates and alkyl polyglycol ether sulfates of the formula RO (CH ₂ -CH ₂ O) _x -SO ₃ H, in which R is a preferably linear alkyl group with 10 to 18 C atoms and x = 0 or 1 to 12,
• Mixtures of surface-active hydroxysulfonates according to DE-A-37 25 030,
• - Sulphated hydroxyalkyl polyethylene and / or hydroxyalkylene propylene glycol ether according to DE-A-37 23 354,
• - Sulfonates of unsaturated fatty acids with 12 to 24 carbon atoms and 1 to 6 dop fur bonds according to DE-A-39 26 344,
• - esters of tartaric acid and citric acid with alcohols, the addition pro products of about 2 to 15 molecules of ethylene oxide and / or propylene oxide Represent fatty alcohols with 8 to 22 carbon atoms.

Preferred anionic surfactants are alkyl sulfates, alkyl polyglycol ether sulfates and ether carboxylic acids with 10 to 18 carbon atoms in the alkyl group and up to 12 glycol ether groups in the molecule and in particular salts of saturated and in particular unsaturated C ₈ -C ₂₂ carboxylic acids, such as oleic acid, stearic acid, isostearic acid and Palmitic acid.

Zwitterionic surfactants are those surface-active compounds which carry at least one quaternary ammonium group and at least one -COO ^(-) - or -SO ₃ ^(-) group in the molecule. Particularly suitable zwitterionic surfactants are the so-called betaines such as the N-alkyl-N, N-dimethylammonium glycinate, for example the cocoalkyl-dimethylammonium glycinate, N-acyl-aminopropyl-N, N-dimethylammonium glycinate, for example the cocoacylaminopropyl-dimethylam monium glycinate, and 2 -Alkyl-3-carboxymethyl-3-hydroxyethyl-imidazofine, each with 8 to 18 carbon atoms in the alkyl or acyl group, and also the cocoacylamino ethylhydroxyethylcarboxymethylglycinate. A preferred zwitterionic surfactant is the fatty acid reamide derivative known under the CTFA name Cocamidopropyl Betaine.

Ampholytic surfactants are surface-active compounds which, in addition to a C _8-18 alkyl or acyl group, contain at least one free amino group and at least one -COOH or -SO ₃ H group in the molecule and are capable of forming internal salts . Examples of suitable ampholytic surfactants are N-alkylglycines, N-alkylpropionic acids, N-alkylamino butyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines, N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids each with about 8 up to 18 carbon atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-cocoalkylaminopropionate, cocoacylaminoethylaminopropionate and C _12-18 acyl sarcosine.

Nonionic surfactants contain z as a hydrophilic group. B. a polyol group, a polyalkylene glycol ether group or a combination of polyol and poly glycol ether group. Such connections are, for example

• - Addition products of 2 to 30 moles of ethylene oxide and / or 0 to 5 moles of pro pylene oxide to linear fatty alcohols with 8 to 22 carbon atoms, to fatty acids with 12 to 22 carbon atoms and alkylphenols with 8 to 15 carbon atoms in the alkyl group,
• C _12-22 fatty acid monoesters and diesters of adducts of 1 to 30 moles of ethylene oxide with glycerol,
• C _{8-22 alkyl} mono- and oligoglycosides and their ethoxylated analogs,
• - Addition products of 5 to 60 moles of ethylene oxide with castor oil and hardened tete castor oil,
• - Addition products of ethylene oxide with sorbitan fatty acid esters
• - Addition products of ethylene oxide with fatty acid alkanolamides.

Examples of those used in the hair treatment compositions according to the invention Cationic surfactants are especially quaternary ammonium compounds. Ammonium halides such as alkyltrimethylammonium chlorides, dial are preferred kyldimethylammoniumchloride and Trialkylmethylammoniumchloride, e.g. B. Cetyltri methyl ammonium chloride, stearyl trimethyl ammonium chloride, distearyl dimethylam monium chloride, lauryldimethylammonium chloride, lauryldimethylbenzylammoni umchloride and tricetylmethylammonium chloride. More ver reversible cationic surfactants are the quaternized protein hydrolyzates.

Cationic silicone oils such as, for example, are also suitable according to the invention shows the commercially available products Q2-7224 (manufacturer: Dow Corning; stabilized trimethylsilylamodimethicone), Dow Corning 929 emulsion (incl tend a hydroxyl-amino-modified silicone, which can also be called amodimethicone is drawn), SM-2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) and Abil®-Quat 3270 and 3272 (manufacturer: Th. Goldschmidt; diquater polydimethylsiloxanes, Quaternium-80).

Alkylamidoamines, especially fatty acid amidoamines such as that under the designation Tego Amid®S 18 available stearylamidopropyldimethylamine, stand out in addition to a good conditioning effect, especially through its good biological Degradability.

Quaternary ester compounds are also very readily biodegradable called "esterquats", such as those sold under the trademark Stepantex® Methylhydroxyalkyldialkoyloxyalkylammonium methosulfates.

An example of a quaternary sugar deri that can be used as a cationic surfactant vat represents the commercial product Glucquat®100, according to the CTFA nomenclature "Lauryl Methyl Gluceth-10 Hydroxypropyl Dimonium Chloride".

The compounds with alkyl groups used as surfactants may vary because they are uniform substances. However, it is usually preferred  in the production of these substances from native vegetable or animal raw substances to go out, so that one mixes substances with different, from receives respective raw material dependent alkyl chain lengths.

In the case of surfactants, the addition products of ethylene and / or propylene oxide of fatty alcohols or derivatives of these adducts can be so probably products with a "normal" homolog distribution as well as those with egg a narrow homolog distribution can be used. Under "normal" Ho Mixtures of homologues are understood to be mixtures of homologues that one in the implementation of fatty alcohol and alkylene oxide using Alkali metals, alkali metal hydroxides or alkali metal alcoholates as catalysts goals. On the other hand, narrow homolog distributions are obtained if for example hydrotalcites, alkaline earth metal salts of ether carboxylic acids, alkaline earth lime metal oxides,

hydroxides or alcoholates can be used as catalysts. The usage of products with a narrow homolog distribution may be preferred.

Other active ingredients, auxiliaries and additives are, for example

• - Non-ionic polymers such as vinyl pyrrolidone-vinyl acrylate copo polymers, polyvinylpyrrolidone and vinylpyrrolidone / vinyl acetate copolymers and Polysiloxanes,
• - Cationic polymers such as quaternized cellulose ethers, polysiloxanes with qua ternary groups, dimethyldiallylammonium chloride polymers, acrylamide di methyldiallylammonium chloride copolymers, Di quaternized with diethyl sulfate methylaminoethyl methacrylate-vinylpyrrolidone copolymers, vinylpyrrolidone- Imidazolinium methochloride copolymers and quaternized polyvinyl alcohol,
• - zwitterionic and amphoteric polymers such as Acrylamidopro pyl-trimethylammonium chloride / acrylate copolymers and octylacrylamide / Me thyl methacrylate tert-butylaminoethyl methacrylate / 2-hydroxypropyl methacrylate Copolymers,
• - Anionic polymers such as polyacrylic acids, cross-linked polyacrylics acids, vinyl acetate / crotonic acid copolymers, vinyl pyrrolidone / vinyl acrylate  Copolymers, vinyl acetate / butyl maleate / sobornyl acrylate copolymers, methyl vinyl ether / maleic anhydride copolymers and acrylic acid / ethyl acrylate / N- tert-butylacrylamide terpolymers,
• Thickeners such as agar agar, guar gum, alginates, xanthan gum, rubber arabicum, karaya gum, locust bean gum, linseed gums, dex trane, cellulose derivatives, e.g. B. methyl cellulose, hydroxyalkyl cellulose and Carboxymethyl cellulose, starch fractions and derivatives such as amylose, Amylopectin and dextrins, clays such as e.g. B. bentonite or fully synthetic Hy drocolloids such as B. polyvinyl alcohol,
• Structurants such as glucose and maleic acid,
• - Hair conditioning compounds such as phospholipids, for example So jalecithin, egg lecithin and cephaline, as well as silicone oils,
• Protein hydrolyzates, in particular elastin, collagen, keratin, milk protein, Soy protein and wheat protein hydrolyzates, their condensation products with fatty acids and quaternized protein hydrolyzates, Perfume oils, dimethyl isosorbide and cyclodextrins,
• - solubilizers such as ethanol, isopropanol, ethylene glycol, propylene glycol, Glycerin and diethylene glycol,
• - anti-dandruff agents such as Piroctone Olamine and Zink Omadine,
• - other substances for adjusting the pH value,
• - Active ingredients such as panthenol, pantothenic acid, allantoin, pyrrolidone carboxylic acids and their salts, plant extracts and vitamins,
• - cholesterol,
• - light stabilizers,
• - consistency enhancers such as sugar esters, polyol esters or polyol alkyl ethers,
• - Fats and waxes such as walrus, beeswax, montan wax, paraffins, fettal alcohols and fatty acid esters,
• - fatty acid alkanolamides,
• Complexing agents such as EDTA, NTA and phosphonic acids, Swelling and penetration substances such as glycerol, propylene glycol monoethyl ether, Carbonates, hydrogen carbonates, guanidines, ureas and primary, sec dare and tertiary phosphates, imidazoles, tannins, pyrrole,  
• Opacifiers such as latex,
• - pearlescent agents such as ethylene glycol mono- and distearate,
• - blowing agents such as propane-butane mixtures, N20, dimethyl ether, CO ₂ and air and
• - antioxidants.

The constituents of the water-containing carrier are used to produce the inventions Colorants according to the invention used in amounts customary for this purpose; e.g. B. emulsifiers in concentrations of 0.5 to 30 wt .-% and Ver thickener in concentrations of 0.1 to 25 wt .-% of the total color used by means.

For the dyeing result, it can be advantageous to add ammonium or add alkali metal salts. Suitable metal salts are e.g. B. Formates, Car bonates, halides, sulfates, butyrates, valemates, capronates, acetates, lactates, Glycolates, tartrates, citrates, gluconates, propionates, phosphates and phosphonates of NH4 +, potassium, sodium or lithium, where sodium acetate, lithium bromide, Ammonium carbonate, chloride and acetate are preferred. These salts are in front preferably in an amount of 0.03 to 65, in particular from 1 to 40, mmol, be added to 100 g of the total colorant.

The pH of the ready-to-use coloring preparations is usually between 2 and 11, preferably between 5 and 9

Another object of the present invention relates to the use of Naphthyl azo compounds of formula I,  

in which R ^{1 represents} hydrogen, halogen, hydroxy, nitro, a C ₁ -C ₄ alkyl group, a C ₁ -C ₄ alkoxy group, sulfo group or carboxy group, R ^{2 represents} a 1- or 2-naphthyl group which has at least one hydroxyl group carries and as further substituents may have hydroxyl, sulfo, carboxy, nitro groups or halogen atoms, or for a 1-aryl-5-hydroxy-4-py razolylrest, which is substituted in the 3-position by a C ₁ -C ₄ group can be stands
M for hydrogen, an alkali or 1/2 alkaline earth metal, 1/3 AI (III), 1l2 Zn (II), 1/4 Ti (IV), 1/4 Zr (IV), 1/3 Cr (III) , 1/2 Co (11), 1/2 Fe (II), 1/3 Mo (111) or 1/6 Mo (VI), 1/3 W (11I) or 1/6 W (VI) or ammonium, as a coloring component in hair dyes.

Yet another object of the present invention relates to a process for dyeing keratin-containing fibers, in particular human hair, in which a colorant containing naphthyl azo compounds of the formula I

in which R ^{1 represents} hydrogen, halogen, hydroxy, nitro, a C ₁ -C ₄ alkyl group, a G ₁ -C ₄ alkoxy group, sulfo group or carboxy group, R ^{2 represents} a 1- or 2-naphthyl group which has at least one hydroxyl group carries and as further substituents may have hydroxyl, sulfo, carboxy, nitro groups or halogen atoms, or for a 1-aryl-5-hydroxy-4-py razolylrest, which is substituted in the 3-position by a C, -C ₄ group can be stands
M for hydrogen, an alkali or 1/2 alkaline earth metal, 1/3 AI (III), 1/2 Zn (II), 1/4 Ti (IV), 1/4 Zr (IV), 1/3 Cr ( III), 1/2 Co (II), 1/2 Fe (II), 1/3 Mo (III) or 1/6 Mo (VI), 1/3 W (III) or 1/6 W ( VI) or ammonium,
as well as usual cosmetic ingredients, placed on the keratin fibers, left for some time, usually about 30 minutes, on the fiber and then rinsed out or washed out with a shampoo.

The above-mentioned metal salts and the as Developer and coupler components known compounds used the.

The naphthyl azo compounds and the other components can either applied to the hair at the same time or one after the other, it is irrelevant which of the components is applied first. It can take up to 30 minutes between the application of the individual components Time interval. Pretreatment of the fibers with a saline solution is also necessary possible.  

Examples Preparation of a coloring solution

0.01 molar solutions of the compounds with the formula I were prepared. Sodium acetate and possibly another salt were added equimolar and with added to a drop of a 20% fatty alkyl ether sulfate solution. The solution was brought to pH 6 with dilute sodium hydroxide solution or hydrochloric acid poses.

A 90% streak of he was in this dyeing solution at 30 ° C for 30 minutes gray, not pretreated human hair. The streak was then rinsed with lukewarm water for 30 seconds, dried with warm air and then combed out.

The respective color shades and depths are shown in Table 1 below reproduced.

The color depth was rated on the following scale:
-: no or a very pale color (+): weak intensity +: medium intensity + (+): medium to strong intensity ++: strong intensity ++ (+): strong to very strong intensity +++: very strong intensity

Table 1

Eriochrome red B dyeings

Table 2

Discolorations with Eriochrome Blue R

Claims (10)

1. agent for dyeing keratin-containing fibers, in particular human hair, containing at least one naphthyl-azo compound with the formula I as the coloring component,
in which R ^{1 represents} hydrogen, halogen, hydroxy, nitro, a, C, -C ₄ alkyl group, a C ₁ -C ₄ alkoxy group, sulfo group or carboxy group,
R ² for a 1- or 2-naphthyl group which carries at least one hydroxyl group and may have hydroxyl, sulfo, carboxy, nitro or halogen atoms as further substituents, or for a 1-aryl-5-hydroxy-4-pyrazolyl radical , which can be substituted in the 3-position by a C ₁ -C ₄ group, M represents hydrogen, an alkali metal or 112 alkaline earth metal, 1/3 AI (III), 1/2 Zn (II), 1 / 4 Ti (IV), 1/4 Zr (IV), 1/3 Cr (III), 1/2 Co (II), 1/2 Fe (II), 1/3 Mo (111) or 1/6 Mo (VI), 1/3 W (LII) or 1/6 W (VI) or ammonium. 2. Composition according to claim 1, characterized in that as compounds with of the formula I eriochrome black A, eriochrome black T, hydroxynaphthol blue, Acid Blue 158, Eriochromrot B, Eriochromrot R, Acid Red 186 or their be any mixtures can be used. 3. Composition according to one of claims 1 to 2, characterized in that the Naphthyl azo compounds of formula I in an amount of 0.03 to 65  mmol, in particular from 1 to 40 mmol, based on 100 g of the total Colorant are included. 4. Agent according to one of claims 1 to 3, characterized in that it additionally one or more metal salts of the 2nd or 3rd main group of the Peri system and / or one or more salts of transition metals ent holds. 5. Composition according to claim 4, characterized in that the metal salts are selected from the group of chlorides, sulfates, acetates, lactates and Ni Ca, Mg, Al (III), Zn (II), Ti (IV), Zr (IV), Cr (III), Co (II), Fe (II), Mo (III, VI), W (III, VI). 6. Agent according to one of claims 1 to 7, characterized in that it additionally oxidation dye precursors and / or substantive dyes from the group of nitrophenylenediamines, nitroaminophenols, anthraquinones or indophenols, preferably in an amount of 0.01 to 20% by weight, be pulled on the entire colorant, contains. 7. Agent according to one of claims 1 to 8, characterized in that it contains oxidizing agents, in particular H ₂ O2, in an amount of 0.01 to 6 wt .-%, based on the application solution. 8. Agent according to one of claims 1 to 9, characterized in that it contains anionic, zwitterionic or nonionic surfactants. 9. Use of naphthyl-azo compounds with the formula I,
in which R 'represents hydrogen, halogen, hydroxy, nitro, a C, -C ₄ alkyl group, a C, -C ₄ alkoxy group, sulfo group or carboxy group,
R2 for a 1- or 2-naphthyl group which carries at least one hydroxyl group and may have hydroxyl, sulfo, carboxy, nitro groups or halogen atoms as further substituents, or for a 1-aryl-5-hydroxy-4-pyrazolyl radical, which can be substituted in the 3-position by a C ₁ -C ₄ group,
M for hydrogen, an alkali or 1/2 alkaline earth metal, 1/3 AI (III), 1/2 Zn (II), 1/4 Ti (IV), 1/4 Zr (IV), 1/3 Cr ( III), 1/2 Co (II), 1/2 Fe (II), 1/3 Mo (III) or 1/6 Mo (VI), 1/3 W (I II) or 1/6 W (VI), or ammonium, is a coloring component in hair dyes. 10. A process for dyeing fibers containing keratin, in particular human hair, in which a colorant containing a naphthyl-azo compound of the formula I
in which R ^{1 represents} hydrogen, halogen, hydroxy, nitro, a C ₁ -C ₄ alkyl group, a C ₁ -C ₄ alkoxy group, sulfo group or carboxy group,
R ² for a 1- or 2-naphthyl group which carries at least one hydroxyl group and may have hydroxyl, sulfo, carboxy, nitro or halogen atoms as further substituents, or for a 1-aryl-5-hydroxy-4-pyrazolyl radical which can be substituted in the 3-position by a C ₁ -C ₄ group,
M for hydrogen, an alkali or 1/2 alkaline earth metal, 1/3 Al (III), 1/2 Zn (II), 1/4 Ti (IV), 1/4 Zr (IV), 1/3 Cr ( III), 1/2 Co (II), 1/2 Fe (II), 1/3 Mo (III) or 1/6 Mo (VI), 1/3 W (III) or 116 W (VI) or ammonium is, as well as usual cosmetic ingredients brought up on the keratin fibers, some time, usually about 30 minutes, left on the fiber and then rinsed out or washed out with a shampoo.